KR20140019309A - Azo compound, dye-based polarizing film, and polarizing plate - Google Patents

Abstract

상기 식에서, A는 치환기를 가질 수 있는 페닐기를 나타내고, R₁∼R₆은 각각 독립적으로, 수소원자, 탄소수 1∼5의 알킬기, 탄소수 1∼5의 알콕시기, 설포기, 또는 설포기를 가지는 탄소수 1∼5의 알콕시기를 나타내고, X는 치환기를 가질 수 있는아미노기, 치환기를 가질 수 있는 벤조일아미노기, 치환기를 가질 수 있는 페닐아미노기, 치환기를 가질 수 있는 페닐아조기, 또는 치환기를 가질 수 있는 나프토트리아졸기를 나타낸다.The present invention relates to an azo compound of Formula (1) or / and a salt thereof, and a polarizing film and a polarizing plate including the same, wherein the polarizing plate of the present invention using the azo compound has a high polarization ratio and high contrast, and a visible light region Color leakage in the lens is excellent, and the optical performance is excellent, the durability is also excellent, and it can use widely in liquid crystal display devices, such as a liquid crystal projector, and others.

In the above formula, A represents a phenyl group which may have a substituent, and R ₁ to R ₆ each independently represent a hydrogen atom, an alkyl group of 1 to 5 carbon atoms, an alkoxy group of 1 to 5 carbon atoms, a sulfo group, or a sulfo group An alkoxy group having 1 to 5 carbon atoms, X represents an amino group which may have a substituent, a benzoylamino group which may have a substituent, a phenylamino group which may have a substituent, a phenylazo group which may have a substituent, or a naphthot which may have a substituent A lipazole group is shown.

Description

Azo compound, dye-based polarizing film and polarizing plate {AZO COMPOUND, DYE-BASED POLARIZING FILM, AND POLARIZING PLATE}

The present invention relates to a novel azo compound, a dye-based polarizing film containing the compound in a polarizing film base film, and a polarizing plate including the polarizing film.

A polarizing plate having a function of transmitting and blocking light is a basic component of a display device such as a liquid crystal display (LCD) together with a liquid crystal having a light switching function. The field of application of LCD has also expanded from small devices such as electronic calculators and clocks to early notebooks, word processors, liquid crystal projectors, liquid crystal televisions, car navigation systems, and indoor and outdoor measuring instruments. Moreover, since a polarizing plate can also be applied to the lens which has a polarizing function, it is applied also to sunglasses with improved visibility, polarizing glasses etc. corresponding to 3D television etc. in recent years. Since the use of the polarizing plate as described above has been widely expanded, the use conditions are also used under a wide range of conditions from low temperature to high temperature, low humidity to high humidity, low light amount to high light amount, and thus have high polarization performance and excellent durability. Polarizing plates are required.

Currently, a polarizing film is used for polarizing film base materials, such as the film of polyvinyl alcohol or its derivative (s) stretched-oriented or the polyene film which produced | generated and orientated polyene by dehydration of the polyvinyl chloride film or the dehydration of a polyvinyl alcohol-type film. It is manufactured by dyeing or containing iodine and a dichroic dye as a dichroic dye. Among these, an iodine polarizing film using iodine as a dichroic dye has excellent polarization performance, but is weak against water and heat, and has a problem in its durability when used for a long time in a high temperature and high humidity state. In order to improve durability, the method of treating with formalin or the aqueous solution containing a boric acid, or using the polymer film with low moisture permeability as a protective film is considered. But the effect is not enough. On the other hand, the dye-based polarizing film using a dichroic dye as the dichroic dye is excellent in moisture resistance and heat resistance as compared to the iodine-based polarizing film, but generally the polarizing performance is not sufficient.

In the neutral color polarizing film formed by adsorbing and aligning several kinds of dichroic dyes on a polymer film, two polarizing films are specified in a wavelength range of visible light in a state where the orientation directions are orthogonal to each other (orthogonal positions). If there is light leakage of a wavelength (color leakage), when the polarizing film is attached to a liquid crystal panel, the color of a liquid crystal display may change in a dark state. In order to prevent it, the transmittance (orthogonal transmittance) of the orthogonal position in the wavelength range of the visible light of the neutral color polarizing film must be equally low.

In addition, in the case of a color liquid crystal projection type display, that is, a color liquid crystal projector, a polarizing plate is used for the liquid crystal image forming portion, but an iodine polarizing plate having a good polarization performance and exhibiting neutral gray has been used. However, since iodine is used as a dichroic dye as mentioned above, an iodine type polarizing plate has a problem that light resistance, heat resistance, and heat and moisture resistance are not enough. In order to solve this problem, the dye-based neutral gray polarizing plate which used the dichroic dye as a dichroic dye has been used. This neutral gray polarizing plate is usually used in combination of pigments of three primary colors in order to averagely improve the transmittance and polarization performance in the entire visible light wavelength range. For this reason, there is a problem that the light transmittance is poor and the light source intensity must be higher in order to brighten the market demand for brighter, such as a color liquid crystal projector. To solve this problem, three polarizing plates corresponding to three primary colors, that is, for the blue channel, for the green channel, and for the red channel, are used.

However, the reduction of the brightness is inevitable due to the large absorption of light by the polarizing plate and the enlargement of an image of a small area of 0.5 to 3 inches to about tens of inches to about several hundreds of inches. Is used. Moreover, in liquid crystal projectors, the desire for further improvement in brightness is deeply rooted, and as a result, the light source intensity to be used has naturally become stronger. As a result, the light and heat applied to the polarizing plate are also increasing.

As a dye used for manufacture of the said dye type polarizing film, the water-soluble azo compound described in patent document 1 to patent document 7 etc. is mentioned, for example.

However, the conventional polarizing plate containing the above water-soluble dye does not sufficiently satisfy the needs of the market in terms of polarization characteristics, absorption wavelength region, color, and the like. In addition, three polarizing plates corresponding to the three primary colors of the color liquid crystal projector, namely for the blue channel, the green channel, and the red channel, are used for brightness and polarization performance, durability in high temperature and high humidity conditions, and for a long time exposure. Not all light resistances are favorable, and the improvement is desired.

Japanese Patent No. 2622748 Japanese Unexamined Patent Publication No. 2001-33627 Japanese Unexamined Patent Publication No. 2004-51645 WO2005 / 075572 WO2007 / 148757 Japanese Laid-Open Patent Publication 2003-327858 Japanese Laid-Open Patent Publication 2005-255846 Japanese Laid-Open Patent Publication 2004-075719

 Dye chemistry; Yoshida Hosoda

One of the objectives of this invention is providing the high performance polarizing plate which has the outstanding polarization performance, moisture resistance, heat resistance, and light resistance. In addition, another object of the present invention is a neutral polarizing plate formed by adsorbing or aligning two or more dichroic dyes onto a polymer film, and having no color leakage at orthogonal in the wavelength range of visible light, and excellent polarization performance and resistance. It is providing the high performance polarizing plate which has wettability, heat resistance, and light resistance.

It is still another object of the present invention to provide a high performance polarizing plate, particularly a color polarizing plate, which has good brightness, polarization performance, durability and light resistance corresponding to three primary colors of a color liquid crystal projector.

MEANS TO SOLVE THE PROBLEM As a result of earnestly researching in order to achieve this objective, the present inventors discovered that the polarizing film and polarizing plate containing a specific azo compound and its salt have the outstanding polarization performance, moisture resistance, heat resistance, and light resistance, and completed this invention. did.

That is, this invention relates to the following invention.

(1) Azo compounds of the following formula (1) or / and salts thereof:

Wherein A represents a phenyl group which may have a substituent, and R ₁ to R ₆ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a sulfo group having 1 to 5 carbon atoms And an alkoxy group of X, X represents a benzoylamino group which may have a substituent, a phenylamino group which may have a substituent, a phenylazo group which may have a substituent, or a naphthotriazole group which may have a substituent.

(2) In (1), X is a benzoylamino group which may have a substituent, a phenylamino group which may have a substituent, a phenylazo group which may have a substituent, or a naphthotriazole group which may have a substituent, and these substituents Is an azo compound or / and its salt which is a C1-C5 alkyl group, a C1-C5 alkoxy group, a hydroxyl group, a carboxy group, a sulfo group, an amino group, or a substituted amino group.

(3) In the above (1) or (2), an azo compound or / and salt thereof, wherein X is a phenylamino group of the following formula (2):

In the above formula, R ₇ and R ₈ each independently represent a hydrogen atom, a methyl group, a methoxy group, a sulfo group, an amino group or a substituted amino group.

(4) The azo compound or / and its salt in any one of said (1)-(3) whose X is the benzoylamino group of following formula (3):

In the formula, R ₉ represents a hydrogen atom, a hydroxyl group, an amino group or a substituted amino group.

(5) The azo compound or / and its salt in any one of said (1)-(4) whose X is a naphthotriazole group of following formula (4):

Wherein m represents 1 or 2.

(6) The azo compound or / and its salt in any one of said (1)-(5) whose X is a phenyl azo group of following formula (5):

In the above formula, R ₁₀ to R ₁₂ each independently represent a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an amino group, or a substituted amino group.

(7) In any one of the above (1) to (6), at least one of the substituents of A is a sulfo group or a carboxy group, and no other substituents are present, or a sulfo group or an alkyl group having 1 to 5 carbon atoms. Azo compound or / and its salt which is a C1-C5 alkoxy group which has a C1-C5 alkoxy group, a sulfo group, a carboxy group, a nitro group, an amino group, or a substituted amino group.

(8) The azo compound or / and its salt in any one of said (1)-(6) whose A is following formula (6):

Wherein R ₁₃ and R ₁₄ each represent a sulfo group, and the other represents a hydrogen atom, a sulfo group, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms.

(9) The azo compound according to any one of (1) to (8), wherein R ₁ to R ₆ each independently represent a hydrogen atom, a methyl group, a methoxy group, a sulfo group, or a C 1-5 alkoxy group having a sulfo group; And salts thereof.

(10) The azo compound or / and its salt which is a formula (7) in any one of (1)-(9):

In said formula, A, R <_1> -R <_6> and X show the same meaning as the thing in Formula (1).

(11) In the above (1) or (10), A is a disulfo substituted phenyl group, R ₂ , R ₄ and R ₆ are each independently a methyl group or a methoxy group, and R ₁ and R ₃ are each independently a hydrogen atom , A methyl group, a methoxy group, or a sulfopropoxy group, R ₅ is a methyl group or a methoxy group, X has an unsubstituted phenylamino group, at least one group selected from the group consisting of a methoxy group, a sulfo group and an amino group as a substituent An azo compound or / and its salt which is a phenylamino group, the benzoylamino group substituted by the amino group, or a disulfo substituted naphthotriazole.

(12) The azo compound or / and its salt according to (11), wherein R ₂ and R ₄ are a methyl group, R ₆ is a methyl group or a methoxy group, and X is an unsubstituted phenyl group or a methoxy substituted phenyl group.

(13) The dye-based polarizing film containing the azo compound in any one of said (1)-(12), and / or its salt in a polarizing film base film.

(14) Dye polarizing film containing at least 1 sort (s) of the azo compound in any one of said (1)-(12), and / or its salt, and at least 1 sort (s) of other organic dye in a polarizing film base film. .

(15) Dye-based polarizing film containing at least two types of azo compounds and / or salts of any of the above (1) to (12) and at least one other organic dye in polarizing film base film. .

(16) The color dye polarizing film containing at least 1 sort (s) of the azo compound in any one of said (1)-(12), and / or its salt in a polarizing film base film.

(17) The dye-based polarizing film according to any one of (13) to (16), wherein the polarizing film base film is a film made of polyvinyl alcohol resin, vinyl alcohol copolymer resin, or polyvinyl alcohol resin modified body.

(18) The dye-based polarizing film according to the above (17), wherein the polarizing film base film is a polyvinyl alcohol resin film.

(19) The dye-based polarizing plate which adhere | attached the transparent protective film on at least one surface of the dye-type polarizing film in any one of said (13)-(18).

(20) Use for manufacturing the liquid crystal display device of the dye-based polarizing film according to any one of the above (13) to (18) or the dye-based polarizing plate according to the above (19).

(21) Use for liquid crystal projector manufacture of the dye-based polarizing film as described in any one of said (13)-(18), or the dye-based polarizing plate as described in said (19).

(22) A liquid crystal display device comprising the dye-based polarizing plate according to the above (19).

The azo compound and its salt of this invention are useful as dye for polarizing films, and have high water solubility. And the polarizing film containing these compounds has the high optical performance (for example, high polarization rate and high contrast) comparable to the polarizing film using iodine, and is excellent also in durability. For this reason, it is suitable for various liquid crystal displays and liquid crystal projectors, vehicle mountings requiring high optical performance and durability, and display applications of industrial weighing instruments that can be used in various environments.

The azo compound or / and its salt of this invention is represented by said Formula (1). In Formula (1), A represents a phenyl group which may have a substituent, R <_1> -R <_6> respectively independently represents a hydrogen atom, a C1-C5 alkyl group, a C1-C5 alkoxy group, a sulfo group, or An alkoxy group having 1 to 5 carbon atoms having a sulfo group, X represents a benzoylamino group which may have a substituent, a phenylamino group which may have a substituent, a phenylazo group which may have a substituent, or a naphthotriazole group which may have a substituent Indicates.

Hereinafter, although the compound of Formula (1) is demonstrated, in the following substituents etc., "lower" means C1-C5, Preferably it is C1-C3.

In Formula (1), A represents the phenyl group which may have a substituent.

Examples of the substituent on the phenyl group in A include a sulfo group, a lower alkyl group, a lower alkoxy group, a lower alkoxy group having a sulfo group, a carboxy group, a sulfo-substituted naphthotriazole group, a nitro group, an amino group, or a substituted amino group.

It is preferable that A has at least 1 sulfo group as a substituent. In the case of having two or more substituents, one of the substituents is a sulfo group or a carboxy group (preferably a sulfo group), and other substituents include lower alkoxy having a sulfo group, a lower alkyl group, a lower alkoxy group, and a sulfo group. Group, carboxy group, nitro group, amino group, or substituted amino group is preferable. As a lower alkoxy group which has the said sulfo group, linear alkoxy is preferable, The substitution position of a sulfo group has preferable alkoxy group terminal, More preferably, they are 3-sulfopropoxy group and 4-sulfobutoxy group. An acetylamino group etc. are mentioned as said substituted amino group. Among the other substituents, a sulfo group, a lower alkyl group or a lower alkoxy group is more preferable.

Moreover, a sulfo group, a methyl group, an ethyl group, a methoxy group, an ethoxy group, a carboxy group, a nitro group, an amino group can also be mentioned as a more preferable substituent of the said other substituent as needed. The number of substituents on the phenyl group in A is preferably 2, and the substitution position is not particularly limited, but a combination of the 2nd and 4th positions is preferable.

In Formula (1), what is represented by following formula (6) as A is preferable.

Wherein R ₁₃ and R ₁₄ each represent a sulfo group, and the other represents a hydrogen atom, a sulfo group, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms.

A more preferable group as A is a disulfophenyl group, most preferably a 2,4-disulfophenyl group.

X represents a benzoylamino group which may have a substituent, a phenylamino group which may have a substituent, a phenylazo group which may have a substituent, or a naphthotriazole group which may have a substituent. X may have a substituent, for example, in the case of a benzoylamino group, a phenylamino group, or a phenylazo group, as the substituent, a lower alkyl group, a lower alkoxy group, a hydroxyl group, a carboxy group, a sulfo group, an amino group or a substituted amino group is preferable. In the case of the naphthotriazole group, the substituent is preferably a sulfo group. An acetylamino group etc. are mentioned as a substituted amino group.

In Formula (1), the group of following formula (2)-(5) is mentioned as a preferable group of X. Moreover, an acetylamino group etc. are mentioned as a substituted amino group in R <_7> -R <_12> in Formula (2), Formula (3), and Formula (5).

Phenylamino group of formula (2):

In the above formula, R ₇ and R ₈ each independently represent a hydrogen atom, a methyl group, a methoxy group, a sulfo group, an amino group or a substituted amino group.

Benzoylamino group of formula (3):

In the formula, R ₉ represents a hydrogen atom, a hydroxyl group, an amino group or a substituted amino group.

Naphthotriazole group of formula (4):

Wherein m represents 1 or 2.

Phenyl azo group of formula (5):

In the formula, each of R ₁₀ to R ₁₂ independently represents a hydrogen atom, a hydroxyl group, a lower alkyl group, a lower alkoxy group, an amino group, or a substituted amino group. Moreover, lower grades represent C1-C5.

When X is a phenylamino group which may have a substituent, the substituent is preferably a methyl group, a methoxy group, an amino group, a substituted amino group (preferably an acetylamino group), or a sulfo group, and more preferably a methyl group, a methoxy group or an amino group. The number and substitution positions of the substituents on the phenyl group are not particularly limited. Usually, as for the number of substituents, 0-2 are preferable, and when substituents other than hydrogen exist, it is preferable that at least 1 substituent exists in p position with respect to the bonding position to an amino group. As a phenylamino group which may have the substituent, the phenylamino group of the said Formula (2) is preferable, and as R <_7> and R <_8>, respectively, a hydrogen atom, a methyl group, a methoxy group, or an amino group is preferable. In Formula (2), when groups other than a hydrogen atom exist, it is preferable that at least 1 exists in p position.

As a phenylamino group which may have a substituent, for example, a phenylamino group, 4-methylphenylamino group, 4-methoxyphenylamino group, 4-aminophenylamino group, 4-amino-2-sulfophenylamino group, 4-amino-3-sulfo A phenylamino group, 4-sulfomethylaminophenylamino group, 4-carboxyethylaminophenylamino group, etc. are mentioned. In these, an unsubstituted phenylamino group and p-methoxyphenylamino group are more preferable.

When X is a benzoylamino group which may have a substituent, the substituent is preferably an amino group, a substituted amino group (preferably an acetylamino group), a hydroxy group, more preferably an amino group and a substituted amino group (preferably an acetylamino group), More preferably, it is an amino group. Although the number and substitution position of the substituent on a phenyl group are not specifically limited, Usually, 0-1 are preferable. When substituents other than a hydrogen atom exist, p position is preferable.

When X is a benzoylamino group, the benzoylamino group of the said Formula (3) is preferable. R ₉ represents a hydrogen atom, a hydroxyl group, an amino group or a substituted amino group, and a hydrogen atom, an amino group or a substituted amino group (preferably an acetylamino group) is preferable. As the substitution position of R _9, the p-position is preferable. As the benzoylamino group, for example, a benzoylamino group, 4-aminobenzoylamino group, 4-hydroxybenzoylamino group or 4- (3-carboxy-1-oxopropylamino) benzoylamino group, 4- (2-carbomethoxy-1 -Oxoethylamino) benzoylamino group, etc. are mentioned. In the benzoylamino group, an aminobenzoylamino group is more preferable.

When X is a naphthotriazole group which may have a substituent, the naphthotriazole group which has a sulfone group of said Formula (4) is preferable. M in Formula (4) represents 1 or 2, and 2 is preferable. As the naphthotriazole, for example, a 6,8-disulfonaftotriazole group, a 7,9-disulfonaphthotriazole group, a 7-sulfonaptotriazole group or a 5-sulfonaptotriazole group, etc. may be mentioned. Can be.

When X is a phenylazo group which may have a substituent, the substituent includes a hydroxy group, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an amino group, or a substituted amino group, and a hydroxy group, an amino group, A methyl group, a methoxy group or a carboxy group is preferable, and a hydroxy group is more preferable. The number of substituents is usually 0-3, Preferably it is 1-2.

When X is the phenyl azo group, the phenyl azo group of the said Formula (5) is preferable. R <_10> -R <_12> in Formula (5) represents a hydrogen atom, a hydroxyl group, a lower alkyl group, a lower alkoxy group, an amino group, or a substituted amino group (preferably acetylamino group) each independently. The number of substituents is preferably 0 to 2, and in some cases 1 is also preferable. It is more preferable that it is a hydroxyl group, an amino group, or a substituted amino group as a substituent. As a phenyl azo group, for example, 2-methylphenyl azo group, 3-methylphenyl azo group, 2, 5-dimethylphenyl azo group, 3-methoxyphenyl azo group, 2-methoxy-5-methylphenyl azo group, 2, 5-dimethoxyphenyl azo group And 4-aminophenyl azo group, 4-hydroxyphenyl azo group, or 4-carboxyethylaminophenyl azo group, etc., but it is preferable that they are 4-aminophenyl azo group, 4-hydroxyphenyl azo group, or 4-carboxyethylaminophenyl azo group. Do.

As X, the group of Formula (2)-(4) is more preferable among the group of said Formula (2)-(5), The phenylamino group of Formula (2) and the naphthotriazole group of Formula (4) are more preferable. , And the phenylamino group of the formula (2) is most preferred.

In formula (1), R <_1> -R <_6> respectively independently mentions a hydrogen atom, a lower alkyl group, a lower alkoxy group, a sulfo group, or a lower alkoxy group (henceforth a sulfo substituted lower alkoxy group) which has a sulfo group. ), And preferably a hydrogen atom, a methyl group, an ethyl group, a methoxy group, an ethoxy group, or a sulfopropoxy group. In addition, the lower alkoxy moiety in the sulfo group-substituted lower alkoxy group is preferably linear, and the substitution position of the sulfo group is preferably an alkoxy group terminal. More preferred sulfo-substituted lower alkoxy groups are 3-sulfopropoxy groups or 4-sulfobutoxy groups. In R <_1> -R <_6> , it is more preferable if it is a hydrogen atom, a methyl group, a methoxy group, or a 3-sulfopropoxy group each independently. As the position of the substituent on the benzene ring of the group other than the hydrogen atom, the bonding position of the azo group on the A side is set to the 1st position, and each benzene ring is independently the 2nd position, the 5th position, the 2nd and 6th positions. A combination, a combination of positions 2 and 5, a combination of positions 3 and 5, and the like. Preferably, only positions 2, only position 5, and positions 2 and 5 are combined. . In addition, in the above, only the 2nd position and only the 5th position show that each benzene ring has one substituent other than a hydrogen atom independently in 2nd position or 5th position.

As a compound which R <_1> -R <_6> substituted by the preferable position, the compound of following formula (7) which is a combination of 2nd position and 5th position is mentioned.

In said formula, A, R <_1> -R <_6> and X show the same meaning as the thing in Formula (1).

As a preferable combination of R <_1> -R <_6> in said Formula (1) or said Formula (7), R <_2> , R <_4> and R <_6> are respectively independently a lower alkyl group or a lower alkoxy group (preferably methyl group or a methoxy group) R ₁ and R ₃ are each independently a hydrogen atom, a lower alkyl group (preferably a methyl group), a lower alkoxy group (preferably a methoxy group), or a sulfo substituted lower alkoxy group (preferably a sulfopropoxy group). And R ₅ is a lower alkyl group or a lower alkoxy group (preferably a methyl group or a methoxy group). In this case, when at least one of R ₁ and R ₃ is a sulfo-substituted lower alkoxy group (preferably sulfopropoxy group), and when R ₁ and R ₃ together are hydrogen atoms, It is preferable, and when R <_1> and R <_3> together are a hydrogen atom, it is more preferable.

In the azo compound of Formula (1), as a preferable compound, the compound of following (I)-(V) is mentioned.

(I) In the formula (1), A is a disulfophenyl group, R ₂ , R ₄ and R ₆ are each independently a lower alkyl group or a lower alkoxy group, R ₁ and R ₃ are each independently a hydrogen atom, a lower alkyl group , A lower alkoxy group, or a sulfo-substituted lower alkoxy group, R 5 is a lower alkyl group or a lower alkoxy group, X is an unsubstituted phenylamino group or a phenylamino group having the following substituent, an unsubstituted benzoylamino group, a benzoylamino group having the following substituent group or An azo compound or / and its salt which is a disulfo substituted naphthotriazole group and the substituent in the phenylamino group which has a substituent, and the benzoylamino group which has a substituent is at least 1 chosen from the group which consists of a sulfo group, a lower alkoxy group, and an amino group.

(II) In the above-mentioned (I), the azo compound or / and its salt as described in said (I) whose compound of Formula (1) is an azo compound of said Formula (7).

(III) The azo compound or / and its salt in (I) or (II) whose at least one of R <_1> and R < ₃ > is a sulfo substituted lower alkoxy group.

(IV) The azo compound or / and its salt in any one of said (I)-(III) whose both R <_1> and R <_3> are hydrogen atoms.

(V) The azo compound or / and its salt in any one of said (I)-(IV) whose lower alkyl group is a methyl group, a lower alkoxy group is a methoxy group, and a sulfo substituted lower alkoxy group is a sulfo substituted propoxy group.

Next, the specific example of the azo compound of the said Formula (1) used by this invention is shown below. In addition, the sulfo group, carboxy group, and hydroxyl group in the said formula are represented by the form of a free acid.

The azo compound of the said Formula (1) and its salt can be manufactured easily by performing well-known diazotization and coupling according to the manufacturing method of the normal azo dye as described in the nonpatent literature 1.

As a specific production method, the above formula (1) aromatic amines corresponding to groups A in (A-NH _2: A has the formula (1) and the same) to diazotization, and the following formula (A) anilines with the primary coupling of And the monoazoamino compound of following formula (B) is obtained.

In the above formula, A, R ₁ and R ₂ represent the same meanings as those in the formula (1).

Subsequently, this monoazoamino compound (B) is diazotized, it is secondary-coupled with the aniline of following formula (C), and the disazoamino compound of following formula (D) is obtained.

In the above formula, A, R ₁ to R ₄ represent the same meanings as those in the formula (1).

This disazoamino compound is diazotized, the third coupling is carried out with aniline of the following formula (E), and the tris azoamino compound of the following formula (F) is obtained.

In the above formula, A, R ₁ to R ₆ represent the same meanings as those in the formula (1).

The azo compound of said Formula (1) is obtained by diazotizing this tris azoamino compound and carrying out quaternary coupling with the naphthol of following formula (G).

In the formula, X represents the same meaning as in formula (1).

In the above reaction, the diazotization step is carried out by dissolving or suspending the diazo component in an aqueous solution of an inorganic acid such as hydrochloric acid or sulfuric acid, and adding nitrite such as sodium nitrite to the obtained liquid mixture and diazotizing, or Nitrite is added to the aqueous solution of a neutral or slightly alkaline diazo component, and it carries out by the reverse method of mixing this and an inorganic acid. As for the temperature of diazotization, -10-40 degreeC is suitable. In the coupling step with the aniline, an acidic aqueous solution such as hydrochloric acid or acetic acid containing aniline and the above diazo solution are mixed, and the temperature is -10 to 40 占 폚 under acidic conditions of pH 2-7.

The mono azo compound disazo compound obtained by coupling, and the tris azo compound may be taken out as it is, or precipitated by acid precipitation or salting out, filtered out, or may proceed to the next step in the state of a solution or a suspension. When the diazonium salt is poorly soluble and in suspension, the diazonium salt may be filtered and used as a press cake in the next coupling step.

In the following, groups such as R ₁ ~R ₆ will be described as including a hydrogen atom, but, for convenience, "substituent".

In the anilines each having one of R ₁ to R ₆ independently as a substituent used in the primary, secondary, and tertiary coupling, a specific method for producing anilines having a sulfo-substituted alkoxy group is generally known. to be. For example, sulfoalkoxy anilines can be obtained by sulfoalkylation and reduction of phenols by the production method described in Patent Document 8, pp35. The obtained compound can be used in the next coupling process.

The quaternary coupling reaction of the diazoside of the tris azoamino compound with the naphthols of the formula (G) is carried out in alkaline conditions from neutral from pH 7 to 10 at a temperature of -10 to 40 ° C. After completion of the reaction, the precipitates are precipitated by salting out, filtered off. Moreover, when refinement | purification is needed, what is necessary is just to repeat salting out or to precipitate from water using an organic solvent. As an organic solvent used for purification, water-soluble organic solvents, such as alcohol, such as methanol and ethanol, and ketones, such as acetone, can be mentioned, for example.

In addition, in this invention, the azo compound of said Formula (1) can use the salt of an azo compound other than being used as a free acid. Such salts include organic salts such as alkali metal salts such as lithium salts, sodium salts and potassium salts, ammonium salts and amine salts. Sodium salts are generally used.

Substituents of the aromatic amines of A-NH _{2 which} are starting materials for synthesizing the azo compound (water-soluble dye) of formula (1) include sulfo groups, lower alkyl groups, lower alkoxy groups, lower alkoxy groups having a sulfo group, carboxyl groups, Substituted naphthotriazole group, nitro group, amino group, or substituted amino group is mentioned. Preferably they are a sulfo group, a lower alkyl group, and a lower alkoxy group. Preferably at least one of the substituents is a sulfo group or a carboxy group, more preferably at least one is a sulfo group. The aromatic amine corresponding to Formula (6) having two substituents is more preferable. In the lower alkoxy group having a sulfo group, the lower alkoxy is preferably linear, and the substitution position of the sulfo group is preferably the terminal of the lower alkoxy group. Here, a lower alkoxy group, Preferably it represents a C1-C5 alkoxyl group, In the lower alkoxy group which has a sulfo group, it is preferable that it is either a 3-sulfopropoxy group or 4-sulfobutoxy group. When A is a phenyl group which has a substituent, when the aromatic amine used as a raw material is illustrated, for example, 4-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 2-aminobenzenesulfonic acid, 4-aminobenzoic acid, 2 -Amino-5-methyl benzenesulfonic acid, 2-amino-5-methoxybenzenesulfonic acid, 4-amino-2-methylbenzenesulfonic acid, 3-amino-4-methoxybenzenesulfonic acid, 2-amino-4 -Sulfobenzoic acid, 2-amino-5-sulfobenzoic acid, 5-aminoisophthalic acid, 2-amino-5-nitrobenzenesulfonic acid, 5-acetamide-2-aminobenzenesulfonic acid, 2-amino-5- ( 3-sulfopropoxy) benzenesulfonic acid, 4-aminobenzene-1,3-disulfonic acid, 2-aminobenzene-1,4-disulfonic acid, etc. are mentioned. Among these, 4-aminobenzenesulfonic acid, 2-amino-5-methoxybenzenesulfonic acid, 4-amino-2-methylbenzenesulfonic acid, and 4-aminobenzene-1,3-disulfonic acid are particularly preferable. Moreover, it may have a naphthotriazole group (of the said Formula (4)) as a substituent on a phenyl group. Examples thereof include a 6,8-disulfonaftotriazole group, a 7,9-disulfonaphthotriazole group, a 7-sulfonaftotriazole group, a 5-sulfonaptotriazole group and the like. In this case, the substitution position is preferably at position p of the phenyl group in A of Formula (1).

As described above as R ₁ to R _{6 in} aniline having substituents (R ₁ to R ₆ ) corresponding to Formula (1), which are primary, secondary, and tertiary coupling components, respectively, a hydrogen atom And lower alkoxy groups having a lower alkyl group, a lower alkoxyl group, or a sulfo group. Preferably it is a hydrogen atom, a methyl group, a methoxy group, or 3-sulfopropoxy group, 4-sulfobutoxy group, More preferably, it is a hydrogen atom, a methyl group, a methoxy group, or 3-sulfopropoxy group. The aniline which has these substituents can have one or two substituents other than a hydrogen atom. In the case of having a substituent other than a hydrogen atom, the bonding position is at positions 2, 3, and 2 and 5, 3 and 5, or 2 and 6 with respect to the amino group. Position 3 and position 2 and position 5 are preferred. Examples of the aniline having a sulfo-substituted lower alkoxyl group include 3- (2-amino-4-methylphenoxy) propane-1-sulfonic acid, 3- (2-aminophenoxy) propane-1-sulfonic acid, and 3- (2 -Amino-4-methylphenoxy) butane-1-sulfonic acid, etc. are mentioned. Examples of the aniline having other substituents include aniline, 2-methylaniline, 3-methylaniline, 2-ethylaniline, 3-ethylaniline, 2,5-dimethylaniline, 2,5-diethylaniline, 2- Methoxyaniline, 3-methoxyaniline, 2-methoxy-5-methylaniline, 2,5-dimethoxyaniline, 3,5-dimethylaniline, 2,6-dimethylaniline or 3,5-dimethoxyaniline, etc. Can be mentioned. These anilines may be protected by an amino group. As a protecting group, the omega-methanesulfone group is mentioned, for example. The anilines used for the primary coupling and the anilines used for the secondary and / or tertiary coupling may be the same or different.

X in naphthol (formula (G)) which has X which is a quaternary coupling component has a phenylamino group which may have a substituent, the benzoylamino group which may have a substituent, the phenylazo group which may have a substituent, or a substituent It is a naphthotriazole group which can be used, and as a substituent, a lower alkyl group, a lower alkoxyl group, a hydroxyl group, a carboxyl group, a sulfone group or an amino group, or a substituted amino group is preferable, respectively. Moreover, about the preferable group of X, it is as having mentioned above in the description of Formula (1).

As naphthol of the said Formula (G), 6-phenylamino-1- naphthol-3- sulfonic acid, naphthol of Formula (72) mentioned later, 6- (4'-methoxyphenylamino) -1-naphthol-3- Sulfonic acid, 6-phenylamino-1-naphthol-3-sulfonic acid, 6- (4'-amino-3'-sulfophenylamino) -1-naphthol-3-sulfonic acid, and the like.

In addition to using the azo compound of the said Formula (1) and its salt individually or in combination for the dye type polarizing film or dye type polarizing plate of this invention, you may use together 1 or more types of other organic dyes as needed. Although there is no restriction | limiting in particular in the other organic dye to combine, It is a dye which has absorption characteristics in the wavelength range different from the absorption wavelength area | region of the azo compound of this invention, or its salt, and a dichroic thing is preferable. For example, C.I. DIRECT Yellow 12, C.I. DIRECT Yellow 28, C.I. DIRECT Yellow 44, C.I. DIRECT Orange 26, C.I. DIRECT Orange 39, C.I. DIRECT Orange 71, C.I. DIRECT Orange 107, C.I. DIRECT Red 2, C.I. DIRECT Red 31, C.I. DIRECT Red 79, C.I. DIRECT Red 81, C.I. DIRECT Red 247, C.I. DIRECT Green 80, C.I. The dye etc. which were described in DIRECT Green 59 and patent documents 1-7 are mentioned as a representative example. It is more preferable to use the dye developed for the polarizing plates described in patent documents 1-7 etc. according to the objective. These dyes are used as free acids or salts of alkali metal salts (for example, Na salts, K salts, Li salts), ammonium salts and amines.

As needed, when using another organic dye together, the kind of dye mix | blended differs by the polarizing film made into the objective by the polarizing film of neutral color, the color polarizing film for liquid crystal projectors, and other color polarizing films, respectively. Although the compounding ratio is not specifically limited, Generally, it is used in the range of 0.1-10 mass parts with the sum of the at least 1 sort (s) or more of said other organic dye based on the mass of the azo compound of Formula (1) and its salt. It is preferable.

The azo compound of Formula (1) and its salt are contained in a polarizing film base material (for example, a polymer film) with other dye as needed by a well-known method, mixed with an alignment seeker, a liquid crystal, or oriented, Or the polarizing film which has various colors or neutral colors can be manufactured by orientating by a coating method. The obtained polarizing film sticks a transparent protective film (or transparent protective layer) to at least one surface, and sets it as a polarizing plate. In the polarizing plate obtained above, a transparent protective layer or an AR (antireflection) layer, a support, and the like are formed as necessary, and a liquid crystal projector, an electronic calculator, a clock, a notebook, a word processor, a liquid crystal television, a car navigation system, and an indoor / outdoor device are provided. It is used for lenses and glasses such as measuring instruments and indicators.

The polarizing film base material (polymer film) used for the dye-based polarizing film of the present invention may be a film made of a polyvinyl alcohol resin or a derivative thereof, and specific examples thereof include polyvinyl alcohol obtained by saponifying polyvinyl acetate or other copolymerization with vinyl acetate. Vinyl alcohol copolymers in which saponified monomers such as C2-C3 olefins such as ethylene and propylene or C3-C4 unsaturated carboxylic acids such as crotonic acid, acrylic acid, methacrylic acid and maleic acid (vinyl alcohol component Preferably at least 50%), and polyvinyl foam or polyvinyl acetal in which polyvinyl alcohol is modified with formaldehyde, acetaldehyde, or the like. Especially, a polyvinyl alcohol film can be used suitably from the point of the adsorptivity and orientation of dye. The thickness of a base material is 30-100 micrometers normally, Preferably it is about 50-80 micrometers.

When the azo compound of Formula (1) or / and its salt is contained in such a polarizing film base material (polymer film), the method of dyeing a polymer film is employ | adopted normally. Staining is performed as follows, for example. First, the azo compound of this invention and / or its salt, and dye other than this are dissolved in water as needed, and a salt bath is prepared. Although dye concentration in a salt bath is not specifically limited, Usually, it selects in about 0.001-10 mass%. In addition, a dyeing aid may be used if necessary, and for example, it is preferable to use forget-me-not at a concentration of about 0.1 to 10% by mass. In this way, the polymer film is immersed in the prepared salt bath for 1 to 10 minutes, and dyeing is performed. Dyeing temperature becomes like this. Preferably it is about 40-80 degreeC.

Orientation of the azo compound of the formula (1) and the salt thereof is carried out by stretching the polymer film dyed as described above or dyeing the stretched polymer film as described above. As a method of extending | stretching, you may use any well-known methods, such as a wet method and a dry method, for example. Stretching of a polymer film can also be performed before dyeing in some cases. In this case, the orientation of the water soluble dye is performed at the time of dyeing. The polymer film containing and aligning the water-soluble dye is subjected to post-treatment such as boric acid treatment by a known method as necessary. This post-treatment is performed for the purpose of improving the light transmittance and the degree of polarization of the polarizing film. Conditions for boric acid treatment vary depending on the type of polymer film used and the type of dye used. Generally, the boric acid concentration of the aqueous solution of boric acid is in the range of 0.1 to 15% by mass, preferably 1 to 10% by mass, and the treatment is in the range of 30 to 80 ° C, preferably 40 to 75 ° C, and 0.5 to 10%. This is done by dipping for a minute. In addition, if necessary, the fixing treatment may be performed together in an aqueous solution containing a cationic polymer compound.

The dye-based polarizing film of this invention obtained in this way can adhere | attach the transparent protective film which was excellent in optical transparency and mechanical strength to the single side | surface or both surfaces, and can be set as a polarizing plate. As a material which forms a protective film, for example, in addition to a cellulose acetate film and an acryl-type film, the resin film which consists of fluorine-type films, such as a tetrafluoroethylene / hexafluoropropylene copolymer, a polyester resin, a polyolefin resin, or a polyamide resin, etc. Can be used. Preferably, a triacetyl cellulose (TAC) film or a cycloolefin type film can be used. The thickness of the protective film is usually 40 to 200 占 퐉.

Examples of the adhesive that can be used to bond the polarizing film and the transparent protective film include polyvinyl alcohol adhesives, urethane emulsion adhesives, acrylic adhesives, polyester-isocyanate adhesives, and the like. Polyvinyl alcohol adhesives are suitable.

You may form a transparent protective layer further on the surface of the dye-type polarizing plate of this invention. As a protective layer, an acryl-type or polysiloxane-type hard coat layer, a urethane type protective layer, etc. are mentioned, for example. Moreover, in order to further improve single-plate light transmittance, it is preferable to form an AR layer on this protective layer. The AR layer can be formed by, for example, depositing or sputtering a material such as silicon dioxide or titanium oxide, or by applying a thin fluorine-based material. Moreover, the dye type polarizing plate of this invention can also be used as an elliptical polarizing plate with a retardation plate.

The dye-based polarizing plate of the present invention thus constructed has no color leakage at orthogonal in the wavelength region of visible light, has excellent polarization performance, and does not cause discoloration or deterioration of polarization performance even at high temperature and high humidity. It is characterized by low light leakage at orthogonal positions.

Further, the dye-based polarizing plate of the present invention preferably has a single plate average light transmittance (wavelength region of 380 to 700 nm, or a specific wavelength range in the color polarizing plate) of 38% or more, preferably 39% or more, more preferably. Preferably it is 40% or more, More preferably, it is 41% or more, and the average light transmittance of a quadrature is 0.4% or less, Preferably it is 0.3% or less, More preferably, it is 0.2% or less, More preferably, it is 0.1% or less.

When making the dye-based polarizing plate of the present invention a polarizing plate having a neutral color such as neutral gray, the polarizing film obtained by a conventional method together with the azo compound of formula (1) is different as shown in the neutral color. A plurality of different dichroic dyes having an absorption maximum in the wavelength range (for example, 2 to 4 kinds) are adsorbed and orientated on the polarizing film base film to obtain a polarizing film having a neutral color, and the polarizing plate as described above. You can get it by doing it.

Moreover, in the case of using a color polarizing plate, according to the target color, for example, blue, green, red, etc., the azo compound of Formula (1) of this invention alone, or another dichroic organic dye as needed. The color polarizing plate which has the target color is used together suitably, and it adsorbs and orients them to a polarizing film base film, makes it a color polarizing film, and makes it a polarizing plate by a conventional method, using suitably as a desired color. You can get it.

In the preferable polarizing plate containing the azo compound of Formula (1) of this invention, a polarization rate is 99.9% or more, and the contrast value is 100 or more, Preferably it is 190 or more, More preferably, it is 300 or more, More preferably, Since is as high as 400 or more, it can be suitably used for various liquid crystal display devices according to the purpose. In addition, since the polarizing plate of the present invention is excellent in durability, the polarizing plate of the present invention can also be suitably used in liquid crystal display devices (liquid crystal display devices, liquid crystal projectors, etc. to be used outdoors) used under severe conditions.

Color polarizing plate in this invention Preferably the color polarizing plate for liquid crystal projectors is a dichroic dye, and contains the azo compound of the said Formula (1) and its salt as needed with the said other organic dye further. . Moreover, the polarizing film used for the color polarizing plate for liquid crystal projectors of this invention is also manufactured by the method described in the part of the manufacturing method of the dye-type polarizing film of this invention mentioned above, It also makes a polarizing plate with a protective film, and if necessary, a protective layer or An AR layer, a support body, etc. can be provided and it can be used as a color polarizing plate for liquid crystal projectors.

As a color polarizing plate for liquid crystal projectors, the wavelength range required for the polarizing plate (A. When an ultra-high pressure mercury lamp is used; 420 to 500 nm for the blue channel, 500 to 580 nm for the green channel, 600 to 680 nm for the red channel, and B. 3 primary LED lamps are used. Peak wavelength in the case of 430-450 nm for a blue channel, 520-535 nm for a green channel, and 620-635 nm for a red channel), wherein the average light transmittance of the single plate is 39% or more, and the average light transmittance of the quadrature is 0.4% or less, More preferably, the single-plate average light transmittance in the required wavelength range of this polarizing plate is 41% or more, and the average light transmittance of orthogonal position is 0.3% or less, More preferably, it is 0.2% or less. More preferably, the single plate average light transmittance in the required wavelength range of the polarizing plate is 42% or more and the average light transmittance of the orthogonal cross section is 0.1% or less. The color polarizing plate for liquid crystal projector of this invention has brightness and the outstanding polarization performance as mentioned above.

In addition, the single-plate average light transmittance is a specific wavelength range (neutral) when natural light is incident on one polarizing plate (hereinafter, only the same meaning is used as a polarizing plate) on which a support such as an AR layer and a transparent glass plate is not provided. It is an average value of the light transmittance in 380-700 nm in color, and the specific wavelength range of the target color in a color polarizing plate. The average light transmittance of the orthogonal position is an average value of the light transmittance in a specific wavelength region when natural light is incident on the two polarizing plates arranged in the orthogonal direction.

In the liquid crystal display device of the present invention, light emitted from a light source such as an ultra-high pressure mercury lamp (UHP lamp), a metal halide lamp, or a white LED passes through the liquid crystal, and the image is displayed on the display screen. The deflection film or the polarizing plate is disposed on either or both of the light source side (incident light side) or the side opposite to the light source (output light side) as viewed from the liquid crystal on the way that the light in the liquid crystal display passes. It may be to pass through the deflection film or the polarizing plate of the present invention formed light.

It is preferable that the color polarizing plate for liquid crystal projectors of this invention formed the said AR layer in the polarizing plate which consists of a polarizing film and a protective film, and made it into the polarizing plate which has an AR layer, and further, the AR layer stuck to support bodies, such as a transparent glass plate, and More preferred is a polarizing plate having a support.

The color polarizing plate for liquid crystal projectors of this invention is normally used as a polarizing plate which has a support body. It is preferable that a support body has a flat part in order to affix a polarizing plate, and a transparent substrate is preferable for an optical use. As a transparent substrate, a glass plate, a lens, a prism (for example, a triangular prism and a cubic prism) is mentioned. What attached the polarizing plate to the lens can be used as a condenser lens with polarized light in a liquid crystal projector. Moreover, attaching a polarizing plate to a prism can be used as a polarizing beam splitter with a polarizing plate in a liquid crystal projector, or a dichroic prism with a polarizing plate. Moreover, it can also stick to a liquid crystal cell. The transparent substrates are broadly divided into inorganic substrates and organic substrates, and inorganic substrates such as soda glass, borosilicate glass, quartz substrate, sapphire substrate, and spinel substrate, and organic substrates such as acrylic and polycarbonate. desirable. The transparent substrate thickness or size may be a desired size. Moreover, in order to further improve single-plate light transmittance, it is preferable to form an AR layer in the polarizing plate with a transparent substrate on one or both surfaces of the glass surface or the polarizing plate surface.

In order to manufacture the color polarizing plate with a support for liquid crystal projectors, a transparent adhesive (adhesive) agent may be applied to, for example, the support plane, and then the dye-based polarizing plate of the present invention may be affixed to this application surface. Moreover, you may apply a transparent adhesive agent (adhesive) to a polarizing plate, and then stick a support body on this application surface. The adhesive (adhesive) agent used here is preferably an acrylic ester type, for example. And when using this polarizing plate as an elliptical polarizing plate, it is common to affix a phase difference plate side to a support body side, but a polarizing plate side can also be affixed on a transparent substrate.

That is, in the color liquid crystal projector using the dye-based polarizing plate of the present invention, the dye-based polarizing plate of the present invention is disposed on either or both of the incident side or the exit side of the liquid crystal cell. Although the polarizing plate may be in contact with the liquid crystal cell, it may not be in contact. However, from the viewpoint of durability, the polarizing plate is preferably not in contact. On the emission side, when the polarizing plate is in contact with the liquid crystal cell, the dye-based polarizing plate of the present invention having the liquid crystal cell as a support can be used. When the polarizing plate is not in contact with the liquid crystal cell, it is preferable to use the dye-based polarizing plate of the present invention using a support other than the liquid crystal cell. From the viewpoint of durability, it is preferable that the dye-based polarizing plate of the present invention is disposed on either the incident side or the emitting side of the liquid crystal cell, and further, the polarizing plate surface of the dye-based polarizing plate of the present invention is placed on the liquid crystal cell side. Is preferably disposed on the light source side. Incidentally, the incident side of the liquid crystal cell refers to the light source side, and the opposite side is called the exit side.

In the color liquid crystal projector using the dye polarizing plate of this invention, it is preferable to arrange | position the ultraviolet cutter filter between the light source and the polarizing plate with the support body of the said incident side. The liquid crystal cell used is, for example, of an active matrix type, and is preferably formed by encapsulating a liquid crystal between a transparent substrate on which an electrode and a TFT are formed and a transparent substrate on which an opposite electrode is formed.

Light emitted from a light source such as an ultra-high pressure mercury lamp (UHP lamp), a metal halide lamp, or a white LED passes through an ultraviolet cutter filter and is separated into three primary colors, and then supports for each channel of blue, green, and red colors. After passing through the color polarizing plate to which it is attached, it is then merged and enlarged by the projection lens and projected onto the screen. Or using blue, green and red LEDs, the light emitted from the respective LEDs is passed through a color polarizing plate to which the support for each channel of blue, green and red is attached, and then coalesced to be enlarged by the projection lens. In addition, a method of projecting onto a screen is also known.

The color polarizing plate for a liquid crystal projector configured as described above is excellent in polarizing performance, and further has a characteristic of not causing discoloration or deterioration in polarizing performance even at high temperature and high humidity.

Example

Hereinafter, although an Example demonstrates this invention still in detail, these are illustrative and do not limit this invention at all. % And parts in the following description are mass references | standards unless there is particular notice.

(Example 1)

25.3 parts of 4-aminobenzene-1,3-disulfonic acid were added to 500 parts of water, and it cooled, and 31.3 parts of 35% hydrochloric acid were added at 10 degrees C or less. Next, 6.9 parts of sodium nitrite was added there, and it stirred at 5-10 degreeC for 1 hour, and diazotized. There, 10.7 parts of 3-methylaniline dissolved in dilute hydrochloric acid was added, sodium carbonate was added to pH3 while stirring at 10-30 degreeC, and it stirred further, and completed the coupling reaction. By filtration, 29.7 parts of monoazoamino compounds of the following formula (69) were obtained.

The obtained monoazoamino compound was added to 400 parts of water and dissolved with sodium hydroxide. At 10-30 degreeC, 25.0 parts of 35% hydrochloric acid were added there, and then 5.5 parts of sodium nitrites were added. The obtained liquid mixture was stirred at 20-30 degreeC for 1 hour, and diazotization was carried out. 8.6 parts of 3-methylaniline dissolved in dilute hydrochloric acid were added thereto, and sodium carbonate was added to pH 3 while stirring at 20 to 30 ° C, and the mixture was further stirred to complete the coupling reaction. By filtration, 31.3 parts of disazoamino compounds of the following formula (70) were obtained.

The obtained disazoamino compound was added to 250 parts of water, and dissolved with sodium hydroxide. At 20-30 degreeC, 20.0 parts of 35% hydrochloric acid were added there, and 4.4 parts of sodium nitrites were added thereafter. It was stirred at 20-30 degreeC for 1 hour, and diazotization was carried out. 7.7 parts of 2,5-dimethylaniline dissolved in dilute hydrochloric acid were added thereto, and sodium carbonate was added to pH 3.5 while stirring at 20-30 degreeC. The mixture was further stirred to complete the coupling reaction. By filtration, 31.8 parts of tris azoamino compounds of following formula (71) were obtained.

The obtained tris azoamino compound was added to 200 parts of water, and dissolved with sodium hydroxide. At 20-30 degreeC, 16.0 parts of 35% hydrochloric acid were added thereafter, 3.5 parts of sodium nitrites were added, it stirred at 20-30 degreeC for 1 hour, and diazotized. On the other hand, 16.1 parts of 6-phenylamino-1-naphthol-3-sulfonic acid of the quaternary coupler were added to 50 parts of water, and dissolved slightly as sodium carbonate. The diazolate of the tris azoamino compound obtained above was injected | poured in this liquid, maintained at pH8-10, stirred, and the coupling reaction was completed. It salted with sodium chloride, and then filtered, and obtained 24.3 parts of tetrakis azo compounds of the said Formula (17). The maximum absorption wavelength of this compound in the 20% aqueous solution of pyridine was 576 nm.

(Example 2)

Example 1 except that 16.1 parts of 6-phenylamino-1-naphthol-3-sulfonic acid of the quaternary coupler were changed to 17.7 parts of 6- (4'-methoxyphenylamino) -1-naphthol-3-sulfonic acid. 25.0 parts of tetrakis azo compounds of the said Formula (16) were similarly obtained. The maximum absorption wavelength of this compound in the 20% pyridine aqueous solution was 579 nm.

(Example 3)

As in Example 1, except that 16.1 parts of 6-phenylamino-1-naphthol-3-sulfonic acid of the quaternary coupler were changed to 18.3 parts of 6- (4'-aminobenzoylamino) -1-naphthol-3-sulfonic acid. Then, 25.4 parts of tetrakis azo compounds of the formula (21) were obtained. The maximum absorption wavelength of this compound in the 20% pyridine aqueous solution was 559 nm.

(Example 4)

Tetrakis azo compound of the formula (20) 30.3 in the same manner as in Example 1, except that 16.1 part of 6-phenylamino-1-naphthol-3-sulfonic acid of the quaternary coupler was changed to 28.2 parts of naphthol of formula (72) Got wealth. The maximum absorption wavelength of this compound in the 20% aqueous solution of pyridine was 575 nm.

(Example 5)

25.3 parts of 4-aminobenzene-1,3-disulfonic acid were added to 500 parts of water, and it cooled. At 10 degrees C or less, 31.3 parts of 35% hydrochloric acid was added there, and then 6.9 parts of sodium nitrite were added, it stirred at 5-10 degreeC for 1 hour, and diazotized. 24.5 parts of 3- (2-amino-4-methyl phenoxy) propane- 1-sulfonic acid which were melt | dissolved in dilute hydrochloric acid were added there, sodium carbonate was added and it made pH3, stirring at 10-30 degreeC. The mixture was further stirred to complete the coupling reaction. By filtration, 40.7 parts of monoazoamino compounds of following formula (73) were obtained.

The obtained monoazoamino compound was added to 400 parts of water, dissolved with sodium hydroxide, 25.0 parts of 35% hydrochloric acid at 10 to 30 ° C, then 5.5 parts of sodium nitrite were added, and stirred at 20 to 30 ° C for 1 hour, Diazotized. To this, 9.7 parts of 2,5-dimethylaniline (secondary coupler) dissolved in dilute hydrochloric acid were added, sodium carbonate was added to pH 3 while stirring at 20 to 30 ° C, and further stirred to complete the coupling reaction, Filtration gave 41.0 parts of disazoamino compounds of the following formula (74).

The obtained disazoamino compound was added to 250 parts of water, and dissolved with sodium hydroxide. At 20-30 degreeC, 20.0 parts of 35% hydrochloric acid were added there, and 4.4 parts of sodium nitrites were added thereafter. It was stirred at 20-30 degreeC for 1 hour, and diazotization was carried out. There, 7.7 parts of 2,5-dimethylaniline dissolved in dilute hydrochloric acid was added, and sodium carbonate was added to pH 3.5 while stirring at 20-30 degreeC. The mixture was further stirred to complete the coupling reaction. By filtering off, 39.6 parts of tris azoamino compounds of following formula (75) were obtained.

The obtained tris azoamino compound was added to 200 parts of water, and dissolved with sodium hydroxide. At 20-30 degreeC, 16.0 parts of 35% hydrochloric acid were added there, and 3.5 parts of sodium nitrites were added thereafter. It stirred at 20-30 degreeC for 1 hour, and diazotized. On the other hand, 17.7 parts of 6- (4'-methoxyphenylamino) -1-naphthol-3-sulfonic acid of the quaternary coupler were added to 50 parts of water, and dissolved slightly as sodium carbonate. The liquid containing the diazo-hydrate of the tris azoamino compound obtained above is injected into this liquid, maintaining at pH8-10, stirring, and completing a coupling reaction. It salted with sodium chloride, filtered and obtained 28.9 parts of tetrakis azo compounds of the said Formula (9). The maximum absorption wavelength of this compound in the 20% aqueous solution of pyridine was 581 nm.

(Example 6)

Same as Example 5, except that 17.7 parts of 6- (4'-methoxyphenylamino) -1-naphthol-3-sulfonic acid of the quaternary coupler were changed to 16.1 parts of 6-phenylamino-1-naphthol-3-sulfonic acid. 28.2 parts of tetrakis azo compounds of said Formula (11) were obtained. The maximum absorption wavelength of this compound in the 20% aqueous solution of pyridine was 578 nm.

(Example 7)

17.7 parts of 6- (4'-methoxyphenylamino) -1-naphthol-3-sulfonic acid of the quaternary coupler 6- (4'-amino-3'-sulfophenylamino) -1-naphthol-3-sulfonic acid Except having changed to 21.0 parts, it carried out similarly to Example 5, and obtained 30.6 parts of tetrakis azo compounds of the said Formula (13). The maximum absorption wavelength of this compound in the 20% aqueous solution of pyridine was 585 nm.

(Example 8)

Other than changing 17.7 parts of 6- (4'-methoxyphenylamino) -1-naphthol-3-sulfonic acid of the quaternary coupler to 18.3 parts of 6- (4'-aminobenzoylamino) -1-naphthol-3-sulfonic acid Was obtained in the same manner as in Example 5 to obtain 29.3 parts of the tetrakis azo compound of Formula (14). The maximum absorption wavelength of this compound in the 20% aqueous solution of pyridine was 567 nm.

(Example 9)

The same procedure as in Example 5 was repeated except that 17.7 parts of 6- (4'-methoxyphenylamino) -1-naphthol-3-sulfonic acid of the quaternary coupler was changed to 28.2 parts of the naphthols of formula (72). 29.1 parts of tetrakis azo compounds of (15) were obtained. The maximum absorption wavelength of this compound in the 20% pyridine aqueous solution was 577 nm.

(Example 10)

17.7 parts of 6- (4'-methoxyphenylamino) -1-naphthol-3-sulfonic acid of the quaternary coupler was changed to 17.6 parts of 6- (4'-hydroxyphenylazo) -3-sulfo-1-naphthol. A 28.9 part of tetrakis azo compounds of the formula (19) were obtained in the same manner as in Example 5 except for the above. The maximum absorption wavelength of this compound in the 20% pyridine aqueous solution was 601 nm.

(Example 11)

28.6 parts of tetrakis azo compounds of the formula (12) were obtained in the same manner as in Example 5 except that 9.7 parts of 2,5-dimethylaniline of the secondary coupler was changed to 8.6 parts of 3-methylaniline. The maximum absorption wavelength of this compound in the 20% aqueous solution of pyridine was 581 nm.

(Example 12)

Except for changing 9.7 parts of 2,5-dimethylaniline of the secondary coupler to 19.6 parts of 3- (2-amino-4-methylphenoxy) propane-1-sulfonic acid, 30.8 parts of tetrakis azo compounds were obtained. The maximum absorption wavelength of this compound in the 20% pyridine aqueous solution was 591 nm.

(Example 13)

Except for changing 24.5 parts of 3- (2-amino-4-methyl phenoxy) propane-1-sulfonic acid of the primary coupler to 13.7 parts of 2-methoxy-5-methylaniline, 26.2 parts of tetrakis azo compounds of 18) were obtained. The maximum absorption wavelength of this compound in the 20% aqueous solution of pyridine was 581 nm.

(Example 14)

24.5 parts of 3- (2-amino-4-methyl phenoxy) propane-1-sulfonic acid of the primary coupler to 12.1 parts of 2,5-dimethylaniline and 9.7 parts of 2,5-dimethylaniline of the secondary coupler 3- (2 28.9 parts of tetrakis azo compounds of the formula (10) were obtained in the same manner as in Example 5, except that 19.6 parts of -amino-4-methylphenoxy) propane-1-sulfonic acid was changed. The maximum absorption wavelength of this compound in the 20% aqueous solution of pyridine was 588 nm.

(Example 15)

24.7 parts of tetrakis azo compounds of the formula (42) were obtained in the same manner as in Example 1 except that 7.7 parts of 2,5-dimethylaniline of the tertiary coupler was changed to 8.7 parts of 2-methoxy-5-methylaniline. The maximum absorption wavelength of this compound in the 20% pyridine aqueous solution was 591 nm.

(Example 16)

7.7 parts of 2,5-dimethylaniline of the tertiary coupler to 8.7 parts of 2-methoxy-5-methylaniline, 16.1 parts of 6-phenylamino-1-naphthol-3-sulfonic acid of the fourth coupler, 30.7 parts of tetrakis azo compounds of the said Formula (43) were obtained like Example 1 except having changed to 28.1 parts of naphthols. The maximum absorption wavelength of this compound in the 20% pyridine aqueous solution was 589 nm.

(Example 17)

From 7.7 parts of 2,5-dimethylaniline of the tertiary coupler to 8.7 parts of 2-methoxy-5-methylaniline and 16.1 parts of 6-phenylamino-1-naphthol-3-sulfonic acid of the fourth coupler 6- (4'- Except having changed into 17.6 parts of methoxyphenylamino) -1-naphthol-3-sulfonic acids, it carried out similarly to Example 1, and obtained 25.4 parts of tetrakis azo compounds of the said Formula (44). The maximum absorption wavelength of this compound in the 20% pyridine aqueous solution was 595 nm.

(Example 18)

25.1 parts of tetrakis azo compounds of the formula (45) were obtained in the same manner as in Example 1 except that 7.7 parts of 2,5-dimethylaniline of the tertiary coupler was changed to 9.7 parts of 2,5-dimethoxyaniline. The maximum absorption wavelength of this compound in the 20% aqueous solution of pyridine was 607 nm.

(Example 19)

Polyvinyl alcohol having a thickness of 75 µm was dipped in an aqueous solution at 45 ° C. at a concentration of 0.03% of the compound of formula (17) obtained in Example 1 and 0.1% of forget-me-not for 4 minutes. The film was stretched 5 times at 50 ° C. in a 3% aqueous boric acid solution, washed with water and dried while maintaining a tension state to obtain a polarizing film.

The maximum absorption wavelength of the obtained polarizing film was 579 nm, polarization rate was 99.9%, and it had a high polarization rate.

In addition, a test method is described below.

The measurement of the maximum absorption wavelength of a polarizing film and calculation of the polarization rate measured and calculated the parallel transmittance and the orthogonal transmittance at the time of polarized light incident using a spectrophotometer (U-4100 by Hitachi Ltd.).

Here, the parallel transmittance (Ky) is the transmittance when the absorption axis of the polarizing film and the absorption axis of the polarizing film are parallel.

Parallel transmittance and orthogonal transmittance of each wavelength were measured at 1 nm intervals at 380 to 780 nm. Using the value measured, respectively, the polarization rate of each wavelength was computed by following formula (i), and the polarization rate at the highest in 380-780 nm and its maximum absorption wavelength (nm) were obtained.

% Polarization = [(Ky-Kz) / (Ky + Kz)] × 100 (i)

(Examples 20 to 36)

Except having made the compound of the said Formula (17) into the azo compound of Examples 2-18, respectively, it carried out similarly to Example 19, and obtained each polarizing film of Examples 20-36. Table 1 shows the maximum absorption wavelength and polarization ratio of each obtained polarizing film.

As shown in Table 1, all the polarizing films created using these compounds had high polarization ratios.

(Example 37)

As an index indicating the quality of an image, there is a contrast indicating a difference in luminance in white display and black display. Table 2 shows the maximum absorption wavelength of the polarizing films obtained in Examples 19 to 29 and 31 to 36 and the contrast at that time.

Here, the contrast represents the ratio of parallel transmittance to orthogonal transmittance (contrast = parallel transmittance at maximum absorption wavelength (Ky) / (orthogonal) transmission at maximum absorption wavelength (Kz)). It shows that the performance is excellent.

In addition, evaluation of contrast (polarization performance) made the sample so that the parallel transmittance of the maximum absorption wavelength of a polarizing film might be equal, and compared. As shown in Table 2, all the polarizing films created using these compounds had high contrast.

(Comparative Example 1)

Instead of the compound of Example 1, using the compound (11) of Patent Document 5 (PTL5) of the following formula, a polarizing film was prepared in the same manner as in Example 19 of the present invention, and Examples 19 to 29 and 31 to 36 Similarly, contrast was calculated.

As shown in Table 2, the compound of this invention showed high contrast with respect to the comparative example 1, and was excellent in polarizing performance.

In addition, the said compound was synthesize | combined similarly to Example 7 of patent document 5.

(Comparative Example 2)

Instead of the compound of Example 1, using the compound (4) of the following patent document 6 (PTL6), the polarizing film was produced like Example 19 of this invention, and the Examples 19-29, and 31-36 and Similarly, contrast was calculated. As shown in Table 2, the compound of this invention showed high contrast with respect to the comparative example 2, and was excellent in polarizing performance. Moreover, the said compound was synthesize | combined similarly to Example 2 of patent document 6.

(Comparative Example 3)

Instead of the compound of Example 1, using the compound (I-3) of Patent Document 7 (PTL7), a polarizing film was prepared in the same manner as in Example 19 of the present invention, and the same as in Examples 19 to 29 and 31 to 36. To calculate the contrast. As shown in Table 2, the compound of this invention showed high contrast with respect to the comparative example 3, and was excellent in polarization performance.

Moreover, the said compound was synthesize | combined similarly to the method described in pp21 of patent document 7.

(Example 37)

On both sides of the polarizing film obtained in Example 25, a triacetyl cellulose film (TAC film; Fujifilm Corporation; trade name TD-80U) was laminated through an adhesive of an aqueous polyvinyl alcohol solution, adhered to glass using an adhesive, and the support was attached. It was made into a polarizing plate. This polarizing plate was irradiated for 190 h with a accelerated xenon arc tester (Suga Test Instruments Co .; SX-75), and the change of the polarization rate before and after irradiation was measured. When the polarization rate change rate was calculated by {(polarization rate before irradiation)-(polarization rate after irradiation)} / (polarization rate before irradiation), the durability excellent in 0.08% was shown.

(Examples 38 to 40, Comparative Examples 4 and 5)

Using the polarizing films obtained in Examples 21, 22 and 24, polarizing plates with a support were prepared in the same manner as in Example 37 (Examples 38 to 40). Moreover, the polarizing plates with a support body were similarly produced using the polarizing films obtained by the comparative examples 1 and 2, respectively (comparative examples 4 and 5).

Light was irradiated to each obtained polarizing plate similarly to Example 37, and the change of the polarization rate before and after light irradiation in each polarizing plate was measured. The results are shown in Table 3.

As is apparent from Table 3, the polarizing plate of the present invention had a smaller polarization rate change rate as compared with the comparative example and showed remarkably excellent durability.

(Example 41)

Compound (17) obtained in Example 1 was prepared with a dye of 0.2%, C.I. Orange 39, 0.07%, C.I. A polarizing film was prepared in the same manner as in Example 19 except that an aqueous solution at 45 ° C. containing Red 81 at a concentration of 0.02% and 0.1% of forget-me-not was used. The maximum absorption wavelength of the obtained polarizing film was 555 nm, the single-plate average light transmittance at 530-570 nm was 42%, and the orthogonal average light transmittance was 0.02%, and it had high polarization degree.

A triacetyl cellulose film (TAC film; Fujifilm Corporation; trade name TD-80U) was affixed on one side of this polarizing film in the same manner as in Example 37, and on the other side, about 10 μm of ultraviolet light on one side of the TAC film. The film in which the hardening | curing hard coat layer was formed was affixed, and the polarizing plate of this invention was obtained. Adhesive of polyvinyl alcohol aqueous solution was used for the sticking of a TAC film. The acrylic ester type adhesive was provided to the surface in which the hard coat layer of the obtained polarizing plate was not formed, and AR (antireflection) multi-coating process was further performed by the vacuum deposition on the outer side of a hard coat layer. The obtained polarizing plate with an AR layer was cut into a size of 30 mm x 40 mm, affixed to a glass plate with a transparent single-sided AR layer of the same size, and a polarizing plate (for a liquid crystal projector green channel) with the AR layer and the support of the present invention. Got. The polarizing plate with the AR layer and the support of the present invention had a high polarization ratio and exhibited durability for a long time even in a state of high temperature and high humidity. In addition, the light resistance against long exposure was excellent.

Claims (22)

Azo compound of Formula (1) or / and its salt:

In this formula,
A represents a phenyl group which may have a substituent,
R ₁ to R ₆ each independently represent a hydrogen atom, a C 1-5 alkyl group, a C 1-5 alkoxy group, or a C 1-5 alkoxy group having a sulfo group,
X represents a benzoylamino group which may have a substituent, a phenylamino group which may have a substituent, a phenylazo group which may have a substituent, or a naphthotriazole group which may have a substituent. The benzoylamino group which may have a substituent, the phenylamino group which may have a substituent, the phenylazo group which may have a substituent, or the naphthotriazole group which may have a substituent, These substituents are C1-C1, An azo compound or / and its salt which is a -5 alkyl group, a C1-C5 alkoxy group, a hydroxyl group, a carboxy group, a sulfo group, an amino group, or a substituted amino group. The azo compound or salt thereof according to claim 1, wherein X is a phenylamino group of formula (2):

In the above formula, R ₇ and R ₈ each independently represent a hydrogen atom, a methyl group, a methoxy group, a sulfo group, an amino group or a substituted amino group. The azo compound or salt thereof according to claim 1, wherein X is a benzoylamino group of formula (3):

In the formula, R ₉ represents a hydrogen atom, a hydroxyl group, an amino group or a substituted amino group. The azo compound or salt thereof according to claim 1, wherein X is a naphthotriazole group of formula (4):

Wherein m represents 1 or 2. An azo compound or salt thereof according to claim 1, wherein X is a phenylazo group of formula (5):

In the above formula, R ₁₀ to R ₁₂ each independently represent a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an amino group, or a substituted amino group. At least one of the substituents of A is a sulfo group or a carboxy group, and there is no other substituent, or a sulfo group, a C1-C5 alkyl group, and carbon number in any one of Claims 1-6. An azo compound or / and its salt which is a C1-C5 alkoxy group which has a 1-5 alkoxy group, a sulfo group, a carboxy group, a nitro group, an amino group, or a substituted amino group. The azo compound or a salt thereof according to any one of claims 1 to 6, wherein A is the following formula (6):

Wherein R ₁₃ and R ₁₄ each represent a sulfo group, and the other represents a hydrogen atom, a sulfo group, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms. The azo compound according to any one of claims 1 to 8, wherein R ₁ to R ₆ each independently represent a hydrogen atom, a methyl group, a methoxy group, a sulfo group, or a C1-5 alkoxy group having a sulfo group; and / or Its salt. The azo compound or a salt thereof according to claim 1, which is the following formula (7):

In the above formula, A, R ₁ to R ₆ and X represent the same meanings as in formula (1). The method according to claim 1 or 10, wherein A is a disulfo substituted phenyl group, R ₂ , R ₄ and R ₆ are each independently a methyl group or a methoxy group, and R ₁ and R ₃ are each independently a hydrogen atom, a methyl group, A methoxy group or a sulfopropoxy group, R ₅ is a methyl group or a methoxy group, X is an unsubstituted phenylamino group, a phenylamino group having at least one group selected from the group consisting of a methoxy group, a sulfo group and an amino group as a substituent, An azo compound or / and its salt which is a benzoylamino group substituted by an amino group, or a disulfo substituted naphthotriazole. The azo compound or / and its salt according to claim 11, wherein R ₂ and R ₄ are a methyl group, R ₆ is a methyl group or a methoxy group, and X is an unsubstituted phenyl group or a methoxy substituted phenyl group. The dye type polarizing film containing the azo compound in any one of Claims 1-12, and / or its salt in a polarizing film base film. The dye type polarizing film containing at least 1 sort (s) of the azo compound in any one of Claims 1-12, and / or its salt, and at least 1 sort (s) of other organic dye in a polarizing film base film. The dye type polarizing film containing at least 2 types of the azo compound in any one of Claims 1-12, and / or its salt, and at least 1 type of other organic dye in a polarizing film base film. The color dye polarizing film containing at least 1 sort (s) of the azo compound and / or its salt in a polarizing film base film. The dye-based polarizing film according to any one of claims 13 to 16, wherein the polarizing film base film is a film made of a polyvinyl alcohol resin, a vinyl alcohol copolymer resin, or a polyvinyl alcohol resin modified body. 18. The dye-based polarizing film according to claim 17, wherein the polarizing film base film is a polyvinyl alcohol resin film. The dye type polarizing plate which adhere | attached the transparent protective film on at least one surface of the dye type polarizing film in any one of Claims 13-18. Use for manufacture of the liquid crystal display device of the dye type polarizing film of any one of Claims 13-18, or the dye type polarizing plate of Claim 19. Use for the liquid crystal projector manufacture of the dye-based polarizing film of any one of Claims 13-18, or the dye-based polarizing plate of Claim 19. A liquid crystal display device comprising the dye-based polarizing plate according to claim 19.